Effects of fluorine substitution in the catechole ring. An ab-initio MO theoretical study

1985 ◽  
Vol 66 (6) ◽  
pp. 395-403 ◽  
Author(s):  
M. Hodoscek ◽  
T. Šolmajer
Keyword(s):  
Ab Initio ◽  
Theoretical Study ◽  
Fluorine Substitution ◽  
Ab Initio Mo

A theoretical study on the reactivity of vinyl iodonium ions

1999 ◽  
Vol 77 (5-6) ◽  
pp. 577-583 ◽  
Author(s):  
Tadashi Okuyama ◽  
Hiroshi Yamataka
Keyword(s):  
Ab Initio ◽  
Theoretical Study ◽  
Chloride Ion ◽  
Medium Effects ◽  
Double Zeta ◽  
Ab Initio Mo ◽  
Vinyl Group ◽  
Dielectric Continuum ◽  
Substituted 1 ◽  
Dielectric Continuum Model

Reactions of methyl(vinyl)iodonium ion and the β-substituted derivatives as well as divinyliodonium ion with chloride ion were examined theoretically by ab initio MO (MP2) calculations at the double-zeta (DZ) + d level. Interaction of the iodonium ion 1 with Cl- leads to chloro-λ3-iodane 2. Transition states for the SN2, ligand-coupling substitution (LC), and β-elimination (βE) are found for reactions at the vinyl group. The barrier to LC is usually the lowest in the gas phase, but relative barriers to SN2 and to βE change with the substituents. Effects of solvent were evaluated by a dielectric continuum model and found to be large on SN2 but small on LC. The experimental observations in solution that the SN2 is the most facile for the β-methyl-substituted 1 while it is retarded by the β-tert-butyl and β-chloro substitutions are reproduced by the calculations that take medium effects into account.Key words: vinyliodonium salt, polyvalent iodine, vinylic SN2 reaction, ligand coupling, ab initio MO calculation.

Theoretical study of the reaction of hydrogen with nitric acid: ab initio MO and TST/RRKM calculations

1997 ◽  
Vol 214 (2-3) ◽  
pp. 219-227 ◽  
Author(s):  
J.W. Boughton ◽  
Sandor Kristyan ◽  
M.C. Lin
Keyword(s):  
Nitric Acid ◽  
Ab Initio ◽  
Theoretical Study ◽  
Ab Initio Mo
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